JP4496114B2 - Solution casting method - Google Patents

Description

  The present invention relates to a solution casting method, and more particularly to a solution casting method for producing a film suitably used for a polarizing plate protective film, an optical compensation film or a photographic photosensitive material base film used in a liquid crystal display device or the like. Is.

  A TAC film formed from cellulose acylate, particularly cellulose triacetate (TAC) having an average degree of acetylation of 57.5% to 62.5% is a support for a film of a photographic photosensitive material because of its toughness and flame retardancy. It is used as a body. Further, since the TAC film is excellent in optical isotropy, it is used for a polarizing plate protective film, an optical compensation film (for example, a viewing angle widening film, etc.) of a liquid crystal display device whose market is expanding in recent years. Yes.

The TAC film is usually produced by a solution casting method. The solution casting method can produce a film having excellent physical properties such as optical properties as compared with other production methods such as a melt casting method. In the solution casting method, a polymer solution (hereinafter referred to as a dope) is prepared by dissolving a polymer in a mixed solvent containing dichloromethane or methyl acetate as a main solvent. The dope is cast on a support by forming a casting bead from a casting die to form a casting film. After the cast film has a self-supporting property on the support, it is peeled off from the support as a film (hereinafter, this film is referred to as a wet film), dried and wound up as a film (for example, (Refer nonpatent literature 1.).
Japan Society for Invention and Innovation Public Technical Bulletin No. 2001-1745

  In recent years, accompanying the increase in film forming speed, accompanying wind generated near the casting bead has become a problem. When the accompanying air is mixed into the casting bead, there is a problem that the air is fired in a later process and the film surface is deteriorated. Further, since the accompanying air strikes the casting bead, the thickness of the casting bead is not constant, and there is a problem that the film thickness is uneven. Therefore, for the purpose of solving these problems, the support surface of the casting bead (hereinafter referred to as the casting bead back surface) is reduced in pressure. In order to keep the back of the casting bead at a reduced pressure, a decompression chamber is installed on the casting die. With the further increase in the film forming speed in recent years, it is necessary to increase the degree of decompression of the back surface of the casting bead (that is, lower the absolute pressure). Therefore, the conventional decompression chamber has a problem that the problem that the accompanying air hits the casting bead cannot be solved.

  Furthermore, in recent years, TAC films have been used as base films for optical functional films. For example, a film having a film thickness of 40 μm, which is thinner than the film thickness of a conventional film of 80 μm, is demanded. In this case, the uniformity of the film thickness is further required. Therefore, it is further required to form the casting bead more stably than the conventional method.

  An object of the present invention is to provide a solution casting method in which the occurrence of thickness unevenness is suppressed and film formation is performed at high speed.

  An object of the present invention is to provide a solution casting method that suppresses occurrence of uneven thickness and forms a thin film at high speed.

This onset Ming, the solution casting method for peeling from the support as a film after cast polymer and solvent and doped to form a bead from the casting die and the support comprising, inside said support a plurality of vacuum chambers are formed by being divided in the direction of movement of the body, using a vacuum chamber that push reduced the support contact surface side of the casting bead, the gap between the support and the decompression chamber 0. Out of the plurality of decompression chambers having a range of 05 mm or more and 3 mm or less and capable of independently adjusting the degree of decompression, the decompression chamber on the upstream side in the moving direction of the support is the decompression chamber on the downstream side. The degree of decompression is lower than that. The gap between the decompression chamber and the support is more preferably in the range of 0.05 mm to 0.7 mm, and most preferably in the range of 0.05 mm to 0.5 mm.

Wherein the maximum value of the absolute pressure in the decompression chamber in the case of the Pn (Pa), the pressure force of the pressure-reducing chamber to the 1 × Pn (Pa) or less in the range 0.9 × Pn (Pa) or higher More preferably, it is preferable to adjust to a range of 0.98 × Pn (Pa) to 1 × Pn (Pa). In the present invention, the pressure means the pressure at the ambient temperature around the die (coating die).

The number of the decompression chambers is preferably 2 or more and 10 or less, and each decompression chamber is preferably provided with an exhaust port.

  The film thickness is preferably 30 μm or more and 120 μm or less, more preferably 30 μm or more and 85 μm or less.

  The polymer is preferably cellulose acylate, more preferably cellulose acetate, and most preferably cellulose triacetate.

  The present invention also includes a film manufactured by the volume film forming method. Moreover, in this invention, it is used preferably for optical functional films, such as a polarizing plate protective film produced from the said film, a base film of a viewing angle expansion film, and the base film of photographic photosensitive materials. Furthermore, a liquid crystal display device constituted by using the optical functional film is also included in the present invention.

  According to the solution casting method of the present invention, a solution casting method in which a dope containing a polymer and a solvent is cast on a support by forming a casting bead from a casting die and then peeled off from the support as a film. In this embodiment, a decompression chamber for reducing the pressure on the support contact surface side of the casting bead is provided, and a gap between the decompression chamber and the support is in a range of 0.05 mm or more and 3 mm or less. It can suppress that a wind hits and it can suppress that the thickness nonuniformity arises in the said film.

  Since the decompression chamber is divided into two sections or more and ten sections or less along the moving direction of the support, it is possible to adjust the degree of decompression on the back surface of the casting bead to a desired range. Occurrence of uneven thickness is further suppressed. In this case, the occurrence of thickness unevenness can be further suppressed by independently adjusting the degree of decompression of each section.

  According to the solution casting method of the present invention, a solution casting method in which a dope containing a polymer and a solvent is cast on a support by forming a casting bead from a casting die and then peeled off from the support as a film. The pressure reducing chamber includes a decompression chamber having a section divided along the moving direction of the support, and the maximum absolute pressure of each section is defined as Pn (Pa). In this case, since the pressure distribution in each section is adjusted to a range of 0.9 × Pn (Pa) to 1 × Pn (Pa), the degree of pressure reduction on the casting bead back surface is adjusted to a desired range. It is possible to suppress the occurrence of uneven thickness in the film.

  According to the solution casting method of the present invention, a solution casting method in which a dope containing a polymer and a solvent is cast on a support by forming a casting bead from a casting die and then peeled off from the support as a film. In the above, a decompression chamber for reducing the pressure on the support contact surface side of the casting bead is provided, and a gap between the decompression chamber and the support is in a range of 0.05 mm or more and 3 mm or less. Since it is divided into 2 sections or more and 10 sections or less along the moving direction, and the degree of decompression of each section is adjusted independently, the maximum value of the absolute pressure of each section is set to Pn (Pa). The pressure distribution in each section can be adjusted to a range of 0.9 × Pn (Pa) to 1 × Pn (Pa), and the casting bead can be formed stably and uniformly. Since the cast film formed from the cast bead is excellent in thickness uniformity, a film obtained by drying the cast film is also excellent in thickness.

  According to the solution casting method of the present invention, the casting bead can be formed stably and uniformly. Moreover, it is suitable for manufacturing a thin film having a film thickness of 30 μm or more and 125 μm or less.

  According to the solution casting method according to the present invention, when cellulose acylate is used as the polymer, it is excellent in optical isotropy and a thin film can be produced. Therefore, it is preferably used for an optical functional film.

  Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments listed here.

[material]
As the cellulose acylate, it is preferable to use a cellulose acylate in which the degree of substitution of the hydroxyl group of cellulose satisfies all of the following formulas (I) to (III). Hereinafter, cellulose acylate satisfying the following formula is referred to as TAC.
(I) 2.5 ≦ A + B ≦ 3.0
(II) 0 ≦ A ≦ 3.0
(III) 0 ≦ B ≦ 2.9
In the formula, A and B represent the substitution degree of the acyl group to the hydrogen atom of the hydroxyl group of cellulose, A is the substitution degree of the acetyl group to the hydrogen atom of the hydroxyl group of cellulose, and B is the carbon to the hydrogen atom of the hydroxyl group of cellulose. It is a substitution degree of an acyl group having 3 to 22 atoms. In addition, it is preferable to use particles having 90% by mass or more of TAC of 0.1 mm to 4 mm. The polymer used in the present invention is not limited to cellulose acylate. The cellulose acylate may be obtained from either linter cotton or pulp cotton, but is preferably obtained from linter cotton.

  Solvents for preparing the dope include aromatic hydrocarbons (eg, benzene, toluene, etc.), halogenated hydrocarbons (eg, dichloromethane, chlorobenzene, etc.), alcohols (eg, methanol, ethanol, n-propanol, n-butanol, Diethylene glycol, etc.), ketones (eg, acetone, methyl ethyl ketone, etc.), esters (eg, methyl acetate, ethyl acetate, propyl acetate, etc.) and ethers (eg, tetrahydrofuran, methyl cellosolve, etc.). In the present invention, the dope means a polymer solution or dispersion obtained by dissolving or dispersing a polymer in a solvent.

  Among these, halogenated hydrocarbons having 1 to 7 carbon atoms are preferably used, and dichloromethane is most preferably used. One kind of alcohol having 1 to 5 carbon atoms in addition to dichloromethane from the viewpoint of physical properties such as solubility of TAC, peelability of cast film from the support, mechanical strength of the film, and optical properties of the film It is preferable to mix several kinds. 2 mass%-25 mass% are preferable with respect to the whole solvent, and, as for content of alcohol, 5 mass%-20 mass% are more preferable. Specific examples of the alcohol include methanol, ethanol, n-propanol, isopropanol, n-butanol and the like, but methanol, ethanol, n-butanol or a mixture thereof is preferably used.

  Recently, a solvent composition not using dichloromethane has been proposed in order to minimize the influence on the environment. Ethers having 4 to 12 carbon atoms, ketones having 3 to 12 carbon atoms, esters having 3 to 12 carbon atoms, and alcohols having 1 to 12 carbon atoms are preferably used. Usually, these are used in an appropriate mixture. For example, a mixed solvent of methyl acetate, acetone, ethanol, and n-butanol can be mentioned. These ethers, ketones, esters and alcohols may have a cyclic structure. A compound having two or more functional groups of ether, ketone, ester and alcohol (that is, —O—, —CO—, —COO—, and —OH) can also be used as the solvent.

  Details of cellulose acylate are described in paragraphs [0140] to [0195] of Japanese Patent Application No. 2004-264464. These descriptions are also applicable to the present invention. In addition, additives such as solvents and plasticizers, deterioration inhibitors, UV absorbers (UV agents), optical anisotropy control agents, retardation control agents, dyes, matting agents, release agents, release accelerators, The details are described in paragraphs [0196] to [0516] of 2004-264464.

[Dope production method]
First, a dope is manufactured using the raw material. First, the solvent is sent to the dissolution tank. Next, the TAC is fed into the dissolution tank while measuring. Thereafter, the additive solution prepared in advance is fed to the required amount dissolution tank. In addition to the method of sending the additive as a solution, for example, when the additive is liquid at room temperature, it is also possible to send the additive to the dissolution tank in the liquid state. Further, when the additive is solid, it can be fed into the dissolution tank using a hopper or the like. When a plurality of types of additives are added, a plurality of types of additives can be dissolved in the additive solution. Alternatively, a solution in which an additive is dissolved can be put in each of a plurality of additive solution tanks, and sent to the dissolution tank through independent pipes.

  The order of putting in the dissolution tank is not limited to the solvent (used in the meaning including the case of the mixed solvent), TAC, and additive. For example, a preferred amount of solvent can be fed after the TAC is metered into the dissolution tank. Further, the additive does not necessarily need to be put in the dissolution tank in advance, and can be mixed in a mixture of TAC and a solvent (hereinafter, these mixtures are also referred to as dope) in a later step.

  The dissolution tank is provided with a jacket and a first stirring blade that is rotated by a motor. Furthermore, it is preferable that the 2nd stirring blade rotated with a motor is attached. The first stirring blade is preferably an anchor blade, and the second stirring blade is preferably a dissolver type. It is preferable to adjust the temperature in the melting tank within a range of -10 ° C to 55 ° C by flowing a heat transfer medium through the jacket. By appropriately selecting and rotating the first stirring blade and the second stirring blade, a swelling liquid in which TAC is swollen in a solvent is obtained.

  The swelling liquid is sent to the heating device by a pump. The heating device is preferably a jacketed pipe, and preferably has a configuration capable of pressurizing the swelling liquid. The dope is obtained by dissolving TAC or the like in a solvent under heating or pressure heating conditions of the swelling liquid. In this case, it is preferable to carry out a method for preparing a dope by heating the swelling liquid to a temperature in the range of 40 ° C. to 120 ° C. (hereinafter referred to as a heating dissolution method). Moreover, the cooling dissolution method which cools a swelling liquid to the temperature of -100 degreeC--30 degreeC can also be performed. TAC can be sufficiently dissolved in a solvent by appropriately selecting the heating dissolution method and the cooling dissolution method. After the temperature of the dope is set to about room temperature with a temperature controller, the dope is filtered to remove impurities in the dope. It is preferable that the average pore diameter of the filtration filter of the filtration device is 100 μm or less. The filtration flow rate is preferably 50 L / hr or more.

  By the way, the method of once preparing a swelling liquid as mentioned above, and making dope with a swelling liquid after that requires time so that the density | concentration of TAC is raised, and a problem may arise in the point of cost. In that case, it is preferable to prepare a dope having a concentration lower than the target TAC concentration, and then perform a concentration step for preparing a dope having the target concentration. When performing such a method, the dope filtered by the filtration device is sent to the flash device. A part of the solvent in the dope is evaporated in a flash apparatus. The evaporated solvent is made liquid by a condenser and then recovered by a recovery device. The recovered solvent is regenerated and reused as a dope preparation solvent by a regenerator. This reuse is effective in terms of cost.

  The concentrated dope is extracted from the flash unit by a pump. Furthermore, it is preferable to perform a bubble removal process to remove bubbles generated in the dope. Any known method may be applied to remove bubbles, for example, an ultrasonic irradiation method. Thereafter, the dope is fed to a filtration device to remove foreign matters. In addition, it is preferable that the temperature of dope at the time of filtration is 0 degreeC-200 degreeC. By these methods, a dope having a TAC concentration of 5% by mass to 40% by mass, preferably 10% by mass to 30% by mass, and most preferably 15% by mass to 25% by mass can be produced.

  [0517] of Japanese Patent Application No. 2004-264464 regarding dope materials, raw materials, methods for dissolving and adding additives, methods for producing dopes such as filtration and defoaming in a solution casting method for obtaining a TAC film The [0616] paragraph is detailed from the paragraph. These descriptions are also applicable to the present invention.

[Solution casting method]
FIG. 1 shows a film production line 10. The film production line 10 includes a filtration device 11, a casting chamber 12, and a tenter dryer 13. Further, an ear clip device 14, a drying chamber 15, a cooling chamber 16 and a winding chamber 17 are arranged.

  The stock tank 20 contains a dope 21 prepared by the above method. A stirring blade 23 that is rotated by a motor 22 is attached. The dope 21 is always made uniform by rotating the stirring blade 23. The stock tank 20 is connected to the filtration device 11 via a pump 24. Additives such as a plasticizer and an ultraviolet absorber can be mixed into the dope 21 in the stock tank 20.

The material of the casting die 30 is preferably a precipitation hardening stainless steel. It is preferable to use a material having a thermal expansion coefficient of 2 × 10 ⁻⁵ (° C. ⁻¹ ) or less. Moreover, what has a corrosion resistance substantially equivalent to the product made from SUS316 by the forced corrosion test by electrolyte aqueous solution can also be used. Further, a material having corrosion resistance that does not cause pitting (opening) at the gas-liquid interface even when immersed in a mixed solution of dichloromethane, methanol, and water for 3 months is used. Furthermore, it is preferable that the casting die 30 is manufactured by grinding a material that has passed one month or more after casting. This prevents the dope from flowing uniformly in the casting die 30 and prevents streaks and the like from occurring in the casting film described later.

  It is preferable to use a liquid contact surface finishing accuracy of the casting die 30 of 1 μm or less in terms of surface roughness and a straightness of 1 μm / m or less in any direction. The slit clearance that can be adjusted in the range of 0.5 mm to 3.5 mm by automatic adjustment is used. About the corner | angular part of the liquid-contact part of the lip tip of the casting die 30, R uses 50 micrometers or less over the full width of a slit. Moreover, it is preferable to use what was adjusted so that the shear rate in the casting die 30 may be set to 1 (1 / sec)-5000 (1 / sec).

  The width of the casting die 30 is not particularly limited, but it is preferable to use a casting die having a width of about 1.01 to 1.3 times the width of the final product. Further, during film formation, it is preferable to attach a temperature controller to the casting die 30 so as to be maintained at a predetermined temperature. The casting die 30 is preferably a coat hanger type. Furthermore, it is more preferable to provide a thickness adjusting bolt (heat bolt) at a predetermined interval in the width direction of the casting die 30 and attach an automatic thickness adjusting mechanism using the heat bolt. The heat bolt is preferably formed by setting a profile according to the amount of pump 24 (preferably a high precision gear pump) according to a preset program. Further, feedback control may be performed by an adjustment program based on a profile of a thickness meter (for example, an infrared thickness meter) (not shown) in the film production line 10. It is preferable that the thickness difference between any two points except the casting edge is adjusted within 1 μm, and the maximum difference in the width direction thickness is adjusted to 3 μm or less. Moreover, it is preferable to use the one whose thickness accuracy is adjusted to ± 1.5 μm or less.

More preferably, a cured film is formed at the lip tip of the casting die 30. A method for forming the cured film is not particularly limited, and examples thereof include ceramic coating, hard chrome plating, and a nitriding method. When ceramics are used as the cured film, those that can be ground, have low porosity, are not brittle, have good corrosion resistance, have good adhesion to the casting die 30, and have no adhesion to the dope are preferable. Specific examples include tungsten carbide (WC), Al ₂ O ₃ , TiN, Cr ₂ O _{3 and the} like, but it is particularly preferable to use WC. The WC coating can be performed by a thermal spraying method.

  In order to prevent the dope flowing out to the slit end of the casting die 30 from locally drying and solidifying, it is preferable to attach a solvent supply device (not shown) to the slit end. Solvent that solubilizes the dope (for example, mixed solvent of 86.5 parts by mass of dichloromethane, 13 parts by mass of acetone, and 0.5 parts by mass of n-butanol). It is preferable to supply to. It is preferable to supply each side of the end portion in a range of 0.1 mL / min to 1.0 mL / min because it is possible to prevent foreign matters from being mixed in the cast film. In addition, it is preferable to use a pump having a pulsation rate of 5% or less for supplying the liquid.

  Below the casting die 30, a rotating drum 31 as a support is provided. The rotating drum 31 is rotated by a driving device (not shown). Further, a heat transfer medium circulation device 32 is attached to the rotating drum 31 in order to set the surface temperature of the rotating drum 31 to a predetermined value. A heat transfer medium flow path (not shown) is formed in the rotary drum 31, and the temperature of the rotary drum 31 is set to a predetermined value by passing through the heat transfer medium maintained at a predetermined temperature. Can be retained. The surface temperature of the rotating drum 31 is not particularly limited, but is preferably −20 ° C. to 40 ° C.

  The width of the rotating drum 31 is not particularly limited, but it is preferable to use a drum having a width in the range of 1.05 to 1.5 times the casting width of the dope. It is preferable to use a surface polished to have a surface roughness of 0.05 μm or less. The material is preferably made of stainless steel, and more preferably made of SUS316 so as to have sufficient corrosion resistance and strength.

In addition, it is also possible to use a casting belt that moves over a rotating roller instead of the rotating drum 31 as a support. In addition, it is necessary to suppress the surface defect of a support body (the rotating drum 31 or a casting band) to the minimum. Specifically, it is preferable that there are no pinholes of 30 μm or more, pinholes of 10 μm or more and less than 30 μm are 1 / m ² or less, and pinholes of less than 10 μm are 2 / m ² or less.

  The casting die 30, the rotating drum 31, etc. are accommodated in the casting chamber 12. In the casting chamber 12, a temperature adjustment facility 33 is attached to keep the temperature in the casting chamber 12 at a predetermined value. It is preferable that the temperature of the casting chamber 12 is −10 ° C. to 57 ° C. In addition, a condenser (condenser) 34 for condensing and recovering the volatile organic solvent is provided. A recovery device 35 for recovering the condensed and liquefied solvent is also provided. The organic solvent condensed and liquefied by the condenser 34 is recovered by the recovery device 35. The solvent is regenerated by a regenerator (not shown) and then reused as a dope preparation solvent. Further, a decompression chamber 36 is attached to the casting die 30 in order to adjust the pressure of the back surface portion of the casting bead that is formed when casting. A decompression device 37 is attached to the decompression chamber 36 so that the degree of decompression can be adjusted. The casting die 30, the decompression chamber 36, and the decompression device 37 will be described in detail later.

  The crossover unit 50 is provided with a blower 51. Further, an ear clip device 14 is provided downstream of the tenter dryer 13. A crusher 53 that finely cuts the waste at the side end (referred to as an ear) of the cut film 52 is connected to the ear clip device 14.

  The drying chamber 15 is provided with a number of rollers 54. An adsorption recovery device 55 is provided for adsorbing and recovering the solvent gas generated by evaporation. Further, a humidity control chamber (not shown) may be provided between the drying chamber 15 and the cooling chamber 16. A forced static elimination device (static elimination bar) 56 for adjusting the charged voltage of the film 52 to be in a predetermined range (for example, −3 kV to +3 kV) is preferably provided downstream of the cooling chamber 16. In FIG. 1, the forced static eliminating device 56 is illustrated on the downstream side of the cooling chamber 16, but is not limited to this position. Furthermore, in this embodiment, it is preferable that a knurling application roller 57 for applying knurling to both edges of the film 52 by embossing is appropriately provided on the downstream side of the forced static elimination device 56. The winding chamber 17 includes a winding roller 58 for winding the film 52 and a press roller 59 for controlling the tension during the winding.

  Next, an example of a method for producing a film using the film production line 10 as described above will be described below. The dope 21 is always made uniform by the rotation of the stirring blade 23. The dope 21 may be mixed with additives such as a plasticizer and an ultraviolet absorber during the stirring.

  The dope 21 is sent to the filtration device 11 by the pump 24 and filtered. Thereafter, as shown in FIG. 2, a casting bead 38 is formed from the casting die 30 and is cast on the rotating drum 31. The speed fluctuation of the rotating drum 31 is preferably 3% or less, and the meandering in the width direction when the rotating drum 31 rotates once is preferably 3 mm or less. It is preferable to adjust the rotational drum 31 immediately below the casting die 30 so that the positional fluctuation in the vertical direction is 500 μm or less. Further, the temperature of the casting chamber 12 is preferably set to −10 ° C. to 57 ° C. by the temperature control equipment 33. The solvent evaporated in the casting chamber 12 is recovered by the recovery device 35 and then regenerated and reused as a dope preparation solvent.

  A casting bead 38 is formed from the casting die 30 to the rotating drum 31, and a casting film 39 is formed on the rotating drum 31. The temperature of the dope 21 at the time of casting is preferably −10 ° C. to 57 ° C. Further, in order to stabilize the casting bead 38, the support contact surface (hereinafter referred to as the casting bead back surface) 38 a of the casting bead 38 is adjusted to a desired pressure value by the decompression chamber 36. The casting bead back surface 38a is preferably decompressed in the range of −2000 Pa to −10 Pa than the air side surface (hereinafter referred to as casting bead front surface) 38b of the casting bead. Further, it is preferable that a jacket (not shown) is attached to the decompression chamber 36 and the temperature is controlled so that the internal temperature is kept at a predetermined temperature. The temperature of the decompression chamber 36 is not particularly limited, but is preferably set to be equal to or higher than the condensation point of the organic solvent used. Further, it is preferable to attach a suction device (not shown) to the edge portion of the casting die 30 in order to keep the shape of the casting bead 38 as desired. The edge suction air volume is preferably in the range of 1 L / min to 100 L / min.

  The decompression chamber 36 includes a first decompression chamber 70, a second decompression chamber 71, a third decompression chamber 72, and a fourth decompression chamber 73 in order from the casting bead back surface 38a. Pumps 74, 75, 76, and 77 are connected to the respective decompression chambers 70 to 73 so that the pressure can be individually adjusted. Pressure gauges 78, 79, 80, 81 and valves 82, 83, 84, 85 are provided between the decompression chambers 70-73 and the pumps 74-77. A controller (not shown) is connected to the pressure gauges 78 to 81. Based on the pressure values measured by the pressure gauges 78 to 81, the controller adjusts the degree of opening and closing of the valves 82 to 85 so that the decompression chambers 70 to 73 are in a desired pressure range. Thereby, the decompression degree of each decompression chamber 70-73 is limited to a desired range.

  In the present invention, the casting bead 38 having excellent surface shape and suppressing thickness unevenness is formed by stabilizing the air flow on the casting bead back surface 38a. The casting film 39 formed from the casting bead 38 has an excellent surface shape and suppresses uneven thickness. Therefore, the film 52 formed from the cast film 39 is excellent in surface shape and thickness unevenness is suppressed. In order to stabilize the air flow, first, the gap CL (mm) between the rotating drum 31 as a support and the decompression chamber 36 is narrowed to suppress the destabilization of the air flow such as the accompanying air. be able to. The narrower the gap CL (mm), the more the atmosphere can be stabilized. The rotating drum 31 is accompanied by fluctuations in the height of the rotating drum surface 31a due to the rotation unevenness. Therefore, the clearance CL (mm) is preferably 0.05 mm or more. In addition, if the upper limit value is 3 mm or less, the atmosphere can be stabilized, but more preferably 0.7 mm or less, and most preferably 0.5 mm or less.

The decompression chamber 36 is preferably divided along the rotation direction of the rotary drum 31 as a support. That is, as shown in FIG. 2, by dividing the decompression chambers 70 to 73 in the moving direction of the support, the accompanying wind is sucked by the fourth decompression chamber 73 on the most upstream side . The accompanying air is sequentially sucked by the third decompression chamber 72 and the second decompression chamber 71 on the downstream side . In this way, the inside and the vicinity of the decompression chamber 70 closest to the casting bead 38 are in a substantially stationary state in which the turbulence of the atmospheric flow is suppressed. Therefore, the decompression degree of the casting bead back surface 38a by the first decompression chamber 70 is stabilized. Therefore, a casting bead 38 having a uniform shape is formed. Along with this, a favorable film shape and uneven thickness of the casting film 39 and the film 52 are obtained.

  The number of decompression chambers is not particularly limited as long as it is a plurality of chambers, but is preferably 2 or more and 10 or less, and most preferably 2 or more and 5 or less. In the present invention, the decompression chamber can be composed of more than 10 decompression chambers, but in that case, the decompression chamber and the decompression device are expensive. Further, when the number of decompression chambers is increased, it may be difficult to adjust the temperature of each decompression chamber. In this case, the solvent that volatilizes from the casting film 39 is likely to cause dew condensation in the decompression chamber 36, which may cause a problem in film production.

  As shown in FIG. 2, the decompression device 37 is configured to independently adjust the pressure in each decompression chamber 70 to 73. In the first decompression chamber 70, a pressure gauge 78, a pressure adjusting valve 82, and a pump 74 are connected. The other decompression chambers 71 to 73 are connected to pressure gauges 79 to 81, valves 83 to 85, and pumps 75 to 77, respectively. The pumps 74 to 77 are not particularly limited, but those having an ultimate vacuum of 0 Pa to 2000 Pa are preferably used. Moreover, in this invention, it is not necessary to attach a pump to each decompression chamber 70-73. For example, each of four vacuum pipes from one pump may be connected to each decompression chamber. In this case as well, it is preferable to attach a valve to each vacuum pipe. Each decompression chamber 70-73 can be made into a desired decompression degree by controlling the open / close degree of each valve.

  In order to prevent pressure fluctuations in the decompression chambers 70 to 73 caused by temperature fluctuations, it is preferable to attach temperature controllers (not shown) to the decompression chambers 70 to 73. By adjusting the temperature of each decompression chamber, the pressure fluctuation accompanying the temperature change can be suppressed. In addition, although the temperature of each decompression chamber 70-73 is not specifically limited, It is preferable that it is the range of 30 to 55 degreeC. If it is lower than 30 ° C, moisture in the atmosphere may be condensed. Moreover, when it exceeds 55 degreeC, there exists a possibility that volatilization of the solvent in the casting bead 38 may advance. In this case, it may be difficult to form the casting bead 38 stably.

By using the device, it is possible to keep the fluctuation of the pressure distribution in each of the decompression chambers 70 to 73 within 5%. That is, when the maximum value of the absolute pressure in the nth decompression chamber is Pn (Pa),
The range is from 0.9 × Pn (Pa) to 1 × Pn (Pa), and the range is from 0.97 × Pn (Pa) to 1 × Pn (Pa) by appropriately selecting a device. In addition, although the pressure distribution in each decompression chamber 70-73 can be measured by a well-known method, it can be measured, for example by Manostar (made by Mihama Corporation).

  The degree of decompression of each decompression chamber 70-73 is not particularly limited. However, the degree of pressure reduction when the atmospheric pressure is 0 Pa is preferably −50 Pa to −1500 Pa, more preferably −200 Pa to −1000 Pa, and most preferably −250 Pa to −800 Pa.

  In the present invention, it is also an effective method to change the degree of decompression of each decompression chamber 70-73. That is, the decompression degree of the fourth decompression chamber 73 farthest from the casting bead 38 where the accompanying air is most likely to be entrained is lowered (that is, the absolute pressure is increased), and the decompression degree is gradually increased toward the casting bead 38 side (ie, By lowering the absolute pressure), it becomes possible to maintain the reduced pressure of the casting bead back surface 38a within a desired range.

The relationship between the decompression degrees of the decompression chambers 70 to 73 is not particularly limited. However, when the degree of pressure reduction P4 of the fourth decompression chamber 73 is −250 Pa or more and −700 Pa or less, the pressure P3 of the third decompression chamber 72; 0.9 × P4 ≦ P3 (Pa) ≦ 1.1 × P4
Pressure P2 in the second decompression chamber 71; 0.9 × P4 ≦ P2 (Pa) ≦ 1.1 × P4
Pressure P1 of the first decompression chamber 70; 0.9 × P4 ≦ P1 (Pa) ≦ 1.1 × P4
It is preferable that the pressure reduction degree of the casting bead back surface 38a can be maintained in a desired range.

  After the casting film 39 has a self-supporting property, it is peeled off from the rotating drum 31 while being supported by the peeling roller 61 as a wet film 60. Thereafter, the transfer section 50 provided with a large number of rollers is conveyed and then fed into the tenter dryer 13. In the crossover part 50, the drying of the wet film 60 is advanced by sending the drying air of desired temperature from the air blower 51. FIG. At this time, the temperature of the drying air is preferably 20 ° C to 250 ° C. In the transition section 50, it is also possible to apply draw tension (tension in the transport direction) to the wet film 60 by making the rotational speed of the downstream roller 62 faster than the rotational speed of the upstream roller 62.

  The wet film 60 sent to the tenter dryer 13 is dried while being transported while being gripped by clips at both edges. Moreover, it is preferable to divide the inside of the tenter dryer 13 into temperature zones and adjust the drying conditions for each of the zones. It is also possible to stretch the wet film 60 in the width direction using the tenter dryer 13. Thus, it is preferable to stretch 0.5% to 300% in at least one of the casting direction and the width direction of the wet film 60 with the crossover 50 and / or the tenter dryer 13.

  The wet film 60 is sent out as a film 52 after being dried to a predetermined residual solvent amount by the tenter dryer 13. Both end portions of the film 52 are cut by the ear clip device 14. The cut film is sent to the crusher 53 by a cutter blower (not shown). The side edges of the film are crushed by the crusher 53 into chips. It is advantageous in terms of cost to reuse this chip for dope preparation. In addition, although the process of cut | disconnecting the both edges of this film can also be abbreviate | omitted, it is preferable to carry out in either from the said casting process to the process of winding up the said film.

  Next, the film 52 is sent to the drying chamber 15 where a number of rollers 54 are provided. Although the temperature in the drying chamber 15 is not specifically limited, It is preferable that it is the range of 50 to 160 degreeC. In the drying chamber 15, the film 52 is conveyed while being wound around the roller 54, and the solvent is volatilized and dried. The solvent (solvent gas) volatilized here is adsorbed and recovered by the adsorption recovery device 55. The air from which the solvent component has been removed by the adsorption recovery device 55 is blown again as dry air inside the drying chamber 15. The drying chamber 15 is more preferably divided into a plurality of sections in order to change the drying temperature. In addition, when a preliminary drying chamber (not shown) is provided between the ear opener 14 and the drying chamber 15 and the film 52 is preliminarily dried, a change in the shape of the film 52 due to a rapid increase in the film temperature in the drying chamber 15 is suppressed. it can.

  The film 52 is cooled to approximately room temperature in the cooling chamber 16. A humidity control chamber (not shown) may be provided between the drying chamber 15 and the cooling chamber 16. Air adjusted to a desired humidity and temperature is blown onto the film 52 in the humidity control chamber. Thereby, generation | occurrence | production of the curling of the film 52 and the winding defect at the time of winding can be suppressed.

  The forced neutralization device (static neutralization bar) 56 sets the charged voltage while the film 52 is being conveyed to a predetermined range (for example, −3 kV to +3 kV). Although the example provided in the downstream of the cooling chamber 16 is shown in FIG. 1, it is not limited to the position. Furthermore, it is preferable to provide a knurling roller 57 and to impart knurling to both edges of the film 52 by embossing. In addition, it is preferable that the unevenness | corrugation of the knurled location is 1 micrometer-200 micrometers.

  Finally, the film 52 is taken up by the take-up roller 58 in the take-up chamber 17. At this time, it is preferable to wind the sheet while applying a desired tension with the press roller 59. More preferably, the tension is gradually changed from the start to the end of winding. The film 52 to be wound is preferably at least 100 m in the longitudinal direction (conveying direction). Further, the width direction is preferably 600 mm or more, and more preferably 1400 mm or more and 1800 mm or less. The present invention is also effective when it is larger than 1800 mm. The thickness of the film can also be applied when producing a thin film having a thickness of 15 μm to 100 μm.

  In the solution casting method of the present invention, when casting dopes, two or more kinds of dopes are simultaneously laminated or sequentially laminated. Furthermore, you may combine both casting. When performing simultaneous lamination and co-casting, a casting die to which a feed block is attached may be used, or a multi-manifold casting die may be used. It is preferable that at least one of the thickness of the layer on the air surface side and the thickness of the layer on the support side is 0.5% to 30% of the thickness of the entire film of the film composed of multiple layers by co-casting. Furthermore, when performing simultaneous lamination co-casting, it is preferable that the high-viscosity dope is wrapped with the low-viscosity dope when casting the dope from the die slit to the support. Moreover, when performing simultaneous lamination co-casting, it is preferable that the dope contacting the outside of the casting bead formed from the die slit to the support has a higher alcohol composition ratio than the inner dope.

  From casting die, vacuum chamber, support structure, co-casting, peeling method, stretching, drying conditions for each process, handling method, curl, winding method after flatness correction, solvent recovery method, film recovery method The details are described in paragraphs [0617] to [0889] of Japanese Patent Application No. 2004-264464. These descriptions are also applicable to the present invention.

[Performance / Measurement method]
(Curl degree / thickness)
The performance of the wound cellulose acylate film and the measuring method thereof are described in paragraphs [0112] to [0139] of Japanese Patent Application No. 2004-264464. These are also applicable to the present invention.

[surface treatment]
It is preferable that at least one surface of the cellulose acylate film is surface-treated. The surface treatment is preferably at least one of vacuum glow discharge treatment, atmospheric pressure plasma discharge treatment, ultraviolet irradiation treatment, corona discharge treatment, flame treatment, acid treatment or alkali treatment.

[Functional layer]
(Antistatic, hardened layer, antireflection, easy adhesion, antiglare)
At least one surface of the cellulose acylate film may be undercoated.

  Furthermore, it is preferable to use the cellulose acylate film as a base film as a functional material provided with another functional layer. The functional layer is preferably provided with at least one layer selected from an antistatic layer, a cured resin layer, an antireflection layer, an easy adhesion layer, an antiglare layer and an optical compensation layer.

The functional layers preferably contain at least one surfactant 0.1mg / m ² ~1000mg / m ² containing. Further, the functional layers preferably contain at least one sort of plasticizers in the 0.1mg / m ² ~1000mg / m ² containing. Further, the functional layers preferably contain at least one sort of matting agents in the 0.1mg / m ² ~1000mg / m ² containing. Further, the functional layers preferably contain at least one sort of antistatic agents 1mg / m ² ~1000mg / m ² containing. In addition to the above, the method for applying a surface-treated functional layer for realizing various functions and properties on the cellulose acylate film is described in detail in paragraphs [0890] to [1087] of Japanese Patent Application No. 2004-264464. It also includes the conditions and methods. These are also applicable to the present invention.

(Use)
The cellulose acylate film is particularly useful as a polarizing plate protective film. A liquid crystal display device is produced by usually providing two polarizing plates each having a cellulose acylate film bonded to a polarizer in a liquid crystal layer. However, the arrangement position of the liquid crystal layer and the polarizing plate is not limited and may be any known position. Japanese Patent Application No. 2004-264464 describes in detail TN type, STN type, VA type, OCB type, reflection type, and other examples of liquid crystal display devices. This method can also be applied to the present invention. The application also describes a cellulose acylate film provided with an optically anisotropic layer and a cellulose acylate film provided with antireflection and antiglare functions. Furthermore, the use as an optical compensation film is also described as a biaxial cellulose acylate film imparting moderate optical performance. This can also be used as a polarizing plate protective film. These descriptions are also applicable to the present invention. Details are described in paragraphs [1088] to [1265] of Japanese Patent Application No. 2004-264464.

  Moreover, the cellulose triacetate film (TAC film) excellent in an optical characteristic can be obtained with the manufacturing method of this invention. The TAC film can be used as a polarizing plate protective film or a base film for a photographic photosensitive material. Furthermore, it can also be used as an optical compensation film for improving the viewing angle dependency of a liquid crystal display device for television applications. In particular, it is effective for applications that also serve as a protective film for a polarizing plate. Therefore, it is used not only for the conventional TN mode but also for the IPS mode, OCB mode, VA mode, and the like. Moreover, you may comprise a polarizing plate using the said film for polarizing plate protective films.

Example 1 will be given below, but the present invention is not limited thereto. The used mass part is shown below.
[composition]
Cellulose triacetate (substitution degree 2.84, viscosity average degree of polymerization 306, water content 0.2 mass%, viscosity 6 mass% in dichloromethane solution 315 mPa · s, average particle diameter 1.5 mm with standard deviation 0.5 mm Some powder) 100 parts by mass dichloromethane (first solvent) 320 parts by mass methanol (second solvent) 83 parts by mass 1-butanol (third solvent) 3 parts by mass plasticizer A (triphenyl phosphate) 7.6 parts by mass Plasticizer B (diphenyl phosphate) 3.8 parts by weight UV agent a: 2 (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole 0.7 part by weight UV agent b: 2 ( 2'-hydroxy-3 ', 5'-di-tert-amylphenyl) -5
Chlorbenzotriazole 0.3 parts by mass Citric acid ester mixture (citric acid, monoethyl ester, diethyl ester, triethyl ester mixture) 0.006 parts by mass fine particles (silicon dioxide (average particle size 15 nm), Mohs hardness about 7) 05 parts by mass

[Cellulose triacetate]
The cellulose triacetate used here has a residual acetic acid content of 0.1% by mass or less, a Ca content of 58 ppm, a Mg content of 42 ppm, a Fe content of 0.5 ppm, free acetic acid of 40 ppm, It contained 15 ppm of sulfate ion. The degree of substitution of the acetyl group with respect to the hydrogen at the 6-position hydroxyl group was 0.91. Further, 32.5% of all acetyl groups were acetyl groups in which the hydrogen of the hydroxyl group at the 6-position was substituted. Moreover, the acetone extraction part which extracted this TAC with acetone was 8 mass%, and the weight average molecular weight / number average molecular weight ratio was 2.5. The obtained TAC has a yellow index of 1.7, a haze of 0.08, a transparency of 93.5%, a Tg (glass transition temperature; measured by DSC) of 160 ° C., and a crystallization calorific value of It was 6.4 J / g. This TAC is synthesized using cellulose collected from cotton as a raw material. In the following description, this is called cotton raw material TAC.

  The plurality of solvents were mixed and stirred well in a 4000 L stainless steel dissolution tank having a stirring blade to obtain a mixed solvent. In addition, as each raw material of a solvent, that whose water content is 0.5 mass% or less was used. Next, TAC flaky powder was gradually added from the hopper. The TAC powder is put into a dissolution tank, and is initially a dissolver type eccentric agitator that stirs at a peripheral speed of 5 m / sec, and a condition in which the center axis has an anchor blade and agitates at a peripheral speed of 1 m / sec. Dispersed for 30 minutes. The temperature at the start of dispersion was 25 ° C., and the final temperature reached 48 ° C. Further, the additive solution prepared in advance was fed to the additive tank so that the total amount was 2000 kg. After finishing the dispersion of the additive solution, the high speed stirring was stopped. Then, the peripheral speed of the anchor blade was set at 0.5 m / sec, and the mixture was further stirred for 100 minutes to swell the TAC flakes to obtain a swelling liquid. Until the end of swelling, the inside of the dissolution tank was pressurized to 0.12 MPa with nitrogen gas. The inside of the dissolution tank at this time was kept in a state where there was no problem in terms of explosion prevention because the oxygen concentration was less than 2 vol%. The amount of water in the swelling liquid was 0.3% by mass.

  The swelling liquid was sent from the dissolution tank to the jacketed pipe using a pump. The swelling liquid was heated to 50 ° C. with a jacketed pipe, and further heated to 90 ° C. under a pressure of 2 MPa to completely dissolve. The heating time at this time was 15 minutes. Next, the temperature of the dissolved liquid was lowered to 36 ° C. with a temperature controller, and the solution was passed through a filtration device having a filter medium having a nominal pore diameter of 8 μm to obtain a dope (hereinafter referred to as a dope before concentration). At this time, the primary pressure in the filtration device was 1.5 MPa, and the secondary pressure was 1.2 MPa. The filters, housings and pipes exposed to high temperatures were made of Hastelloy (trade name) alloy and had excellent corrosion resistance, and were equipped with a jacket for circulating a heat transfer medium for heat insulation and heating.

The pre-concentration dope thus obtained was flash evaporated in a flash device at 80 ° C. and normal pressure, and the evaporated solvent was recovered by a condenser. The solid concentration of the dope after flashing was 22.5% by mass. The condensed solvent was recovered with a recovery device to be reused as a dope preparation solvent. Then, after regenerating with a regenerator, the solution was sent to a solvent tank. Distillation and dehydration were performed in the recovery device and the regeneration device. The flash tank of the flash device was provided with a stirrer having an anchor blade on the stirring shaft, and the dope flashed at a peripheral speed of 0.5 m / sec was stirred by the stirrer to perform defoaming. The temperature of the dope in this flash tank was 25 ° C., and the average residence time of the dope in the tank was 50 minutes. The shear viscosity of this dope taken and measured at 25 ° C. was 450 Pa · s at a shear rate of 10 (sec ⁻¹ ).

  Next, bubble removal was performed by irradiating the dope with weak ultrasonic waves. Thereafter, the filter was passed through the pump while being pressurized to 1.5 MPa using a pump. In the filtration apparatus, first, a sintered fiber metal filter having a nominal pore diameter of 10 μm was passed, and then a sintered fiber filter having a same pore diameter of 10 μm was passed. Respective primary pressures were 1.5 MPa and 1.2 MPa, and secondary pressures were 1.0 MPa and 0.8 MPa. The dope temperature after filtration was adjusted to 36 ° C., and the dope 21 was fed into a 2000 L stainless steel stock tank 20 and stored. The stock tank 20 has a stirrer having an anchor blade 23 on the central axis, and was constantly stirred at a peripheral speed of 0.3 m / sec. In addition, when the dope was prepared from the dope before concentration, no problem such as corrosion occurred at all in the wetted part of the dope. The dope produced by the above method is referred to as dope A.

  A film was produced using the film production line 10 shown in FIG. The dope 21 in the stock tank 20 was sent to the filtration device 11 with a high-precision gear pump 24. The gear pump 24 has a function of increasing the pressure on the primary side of the pump 24, and sends the liquid by performing feedback control on the upstream side of the gear pump 24 with an inverter motor so that the pressure on the primary side becomes 0.8 MPa. . A gear pump 24 having a volume efficiency of 99.2% and a discharge rate variation rate of 0.5% or less was used. The discharge pressure was 1.5 MPa. Then, the dope 21 that passed through the filtration device 11 was fed to the casting die 30.

  A casting die 30 having a width of 1.8 m was used. Further, casting was performed by adjusting the flow rate of the dope 21 at the discharge port of the casting die 30 so that the film thickness of the dried film was 40 μm. The casting width of the dope 21 from the discharge port of the casting die 30 was 1700 mm. In order to adjust the temperature of the dope 21 to 36 ° C., a jacket (not shown) was provided on the casting die 30, and the temperature of the casting die 30 was adjusted to be 30 ° C. to 40 ° C.

  The casting die 30 and the piping were all kept at 36 ° C. during film formation. The casting die 30 was a coat hanger type die. The casting die 30 was provided with thickness adjusting bolts at a pitch of 20 mm and equipped with an automatic thickness adjusting mechanism using heat bolts. This heat bolt can also set a profile according to the liquid feed amount of the gear pump 24 by a preset program, and is fed back by an adjustment program based on a profile of an infrared thickness meter (not shown) installed in the film production line 10. The thing which has the performance which can be controlled was used. In the film excluding the edge 20 mm, the thickness difference between two arbitrary points 50 mm apart was within 1 μm, and the thickness variation in the width direction was adjusted to 3 μm / m or less. The overall thickness was adjusted to ± 1.5% or less.

  On the primary side of the casting die 30, a decompression chamber 36 for decompressing this portion was installed. The degree of decompression of the decompression chamber 36 was adjusted so that the decompression of the casting bead back surface 38a was 300 Pa lower than the atmospheric pressure in terms of absolute pressure (the degree of decompression was −300 Pa). The maximum decompression degree P1 of the first decompression chamber 70 is -500 Pa, the maximum decompression degree P2 of the second decompression chamber 71 is -500 Pa, the maximum decompression degree of the third decompression chamber 72 is -500 Pa, and the maximum of the fourth decompression chamber 73 is The degree of vacuum was adjusted to be −500 Pa. And the pressure reduction degree of the nth decompression chambers 70-73 was adjusted so that it might become 0.9xPn or more and 1xPn or less. Further, the clearance CL between the decompression chamber 36 and the rotating drum surface 31a was set to 0.5 mm. The temperature of the decompression chamber 36 was adjusted to be 35 ° C to 50 ° C. Labyrinth packings (not shown) were provided on the front and back portions of the beads at the casting die discharge port. Further, openings were provided at both ends of the die discharge port of the casting die 30. Further, an edge suction device (not shown) for adjusting the disturbance of both edges of the casting bead was attached to the casting die 30.

The material of the casting die 30 was precipitation hardening type stainless steel, and the material had a thermal expansion coefficient of 2 × 10 ⁻⁵ (° C. ⁻¹ ) or less. In a forced corrosion test with an aqueous electrolyte solution, the material had a corrosion resistance substantially equivalent to that of SUS316. Further, even when immersed in a mixed solution of dichloromethane, methanol and water for 3 months, it had corrosion resistance that did not cause pitting (opening) at the gas-liquid interface. The finishing accuracy of the liquid contact surface of the casting die 30 was 1 μm or less in terms of surface roughness, the straightness was 1 μm / m or less in any direction, and the slit clearance was adjusted to 1.5 mm. About the corner | angular part of the liquid-contact part of the lip tip of the casting die 30, what was processed so that R might be set to 50 micrometers or less over the full width of a slit was used. The shear rate of the dope 21 inside the casting die 30 was in the range of 1 (1 / sec) to 5000 (1 / sec). Further, a WC (tungsten carbide) coating was performed on the lip end of the casting die 30 by a thermal spraying method to provide a cured film.

  Further, a mixed solvent (dichloromethane: methanol = 50 parts by mass: 50 parts by mass) for solubilizing the dope 21 is provided at the discharge port of the casting die 30 in order to prevent the outflowing dope 21 from locally drying and solidifying. Part) was supplied to the interface between the both ends of the casting bead 38 and the discharge port at a rate of 0.5 ml / min. The pulsation rate of the pump supplying the mixed solvent was 5% or less. Further, the pressure on the casting bead back surface 38a side was reduced by 300 Pa (the pressure reduction degree was −300 Pa) from the pressure on the casting bead front surface 38b by the decompression chamber 36. A jacket (not shown) was attached to make the internal temperature of the decompression chamber 36 constant at a predetermined temperature. A heat transfer medium adjusted to 35 ° C. was supplied into the jacket. The edge suction device can adjust the edge suction air volume so as to be in the range of 1 L / min to 100 L / min, and in the present embodiment, this is in the range of 30 L / min to 40 L / min. Was adjusted accordingly.

  A rotating drum 31 having a diameter of 3 m and a width of 1.5 m was used as a support. The surface material of the rotating drum 31 is chrome-plated and has sufficient corrosion resistance and strength. Moreover, it grind | polished so that the surface roughness might be 0.05 micrometer or less. A liquid flow path was formed in the rotating drum 31. A heat transfer medium circulation device 32 for supplying the heat transfer medium to the liquid flow path was attached. The surface temperature of the rotating drum 31 was kept below 0 ° C. Further, the rotational distance between the lip of the casting die 30 and the rotating drum 31 when the rotating drum 31 makes one rotation (usually the position where the dope is cast) is arranged to be 500 μm or less. The rotating drum 31 was installed in the casting chamber 12 having wind pressure fluctuation suppressing means (not shown). The dope 21 was cast from the casting die 30 onto the rotating drum 31.

The rotary drum 31 preferably has no surface defects, pinholes or 30μm is none, the pinhole 10 m to 30 m 1 pieces / m ² or less, pin holes of less than 10μm is two / m ² or less The thing which is is used.

  The temperature of the casting chamber 12 was kept at 35 ° C. using the temperature control equipment 33. The cast film 39 was dried by sending dry air. The saturation temperature of the drying wind was around −8 ° C. The oxygen concentration in the dry atmosphere on the rotating drum 31 was kept at 5 vol%. In order to maintain this oxygen concentration at 5 vol%, the air was replaced with nitrogen gas. Further, in order to condense and recover the solvent in the casting chamber 12, a condenser (condenser) 34 was provided, and its outlet temperature was set to -10 ° C.

  A wind shield (not shown) is installed so that the dry wind does not directly hit the casting bead 38 and the casting film 39 for 5 seconds after casting, and the static pressure fluctuation in the immediate vicinity of the casting die 30 is ± 1 Pa. The following were suppressed. When the solvent ratio in the cast film 39 reached 200% by mass on a dry basis, the film was peeled off as the wet film 60 while being supported by the peeling roller 61 from the rotary drum 31. The solvent content on the basis of the dry weight is a value calculated by {(xy) / y} × 100, where x is the film weight at the time of sampling and y is the weight after drying the sampling film. It is. In order to suppress the peeling failure, the peeling speed (peeling roller draw) with respect to the speed of the rotating drum 31 was appropriately adjusted in the range of 103% to 120%. The solvent gas generated by the drying was condensed and liquefied by a condenser 34 at −10 ° C. and recovered by a recovery device 35. The recovered solvent was adjusted so that the water content was 0.5% or less. The drying air from which the solvent was removed was heated again and reused as drying air.

  The wet film 60 was conveyed through the roller 62 of the cross section 50 and sent to the tenter dryer 13. In the crossover portion 50, dry air was blown from the blower 51 to the wet film 60. The surface material of the roller 62 was made of Teflon (registered trademark), and the surface temperature was adjusted to 20 ° C. or less.

  The wet film 60 sent to the tenter dryer 13 was transported through the drying zone of the tenter dryer 13 while being fixed at both ends with clips, and was dried by drying air during this time. The clip was cooled by supplying a heat transfer medium at 20 ° C. The clip was conveyed by a chain, and the speed fluctuation of the sprocket was 0.5% or less. Further, the inside of the tenter dryer 13 was divided into three zones, and the drying air temperature of each zone was set to 90 ° C., 110 ° C., and 120 ° C. from the upstream side. The gas composition of the drying air was set to a saturated gas concentration at −10 ° C. The conditions of the drying zone were adjusted so that the amount of residual solvent in the film 52 was 10% by mass at the outlet of the tenter dryer 13. The tenter dryer 13 was also stretched in the width direction while being conveyed. In addition, when the width | variety of this wet film 60 before extending | stretching was 100%, it extended | stretched so that the width | variety after extending | stretching might be 105%. The stretching ratio in the tenter dryer 13 is any two at a difference of 10% or less between each of the substantial stretching ratios at any two points at a position 10 mm or more away from the biting start position by the clip and at a distance of 20 mm. The difference in the stretching ratio of points was 5% or less. The ratio of the length from the clip clamping start position to the clamping release position with respect to the length from the inlet to the outlet of the tenter dryer 13 was 90%. The solvent evaporated in the tenter dryer 13 was condensed and liquefied at a temperature of −10 ° C. and recovered. A condenser (condenser) was provided for condensation recovery, and the outlet temperature was set to -8 ° C. The condensed solvent was reused after adjusting the water content to 0.5% by mass or less. And it sent out from the tenter type dryer 13 as the film 52.

Then, the ear-cutting device 14 cuts off both ends of the film 52 within 30 seconds from the outlet of the tenter dryer 13. Ears 50 mm on both sides were cut with an NT-type cutter, and the cut ears were blown to a crusher 53 with a cutter blower (not shown) and crushed into chips of about 80 mm ² on average. This chip was used again as a raw material for dope production together with TAC flakes as a raw material for dope preparation. The oxygen concentration in the drying atmosphere of the tenter dryer 13 was maintained at 5 vol%. Note that the air was replaced with nitrogen gas in order to maintain the oxygen concentration at 5 vol%. Before drying at a high temperature in the drying chamber 15 described later, the film 52 was preheated in a predrying chamber (not shown) supplied with 100 ° C. drying air.

  The film 52 was dried at high temperature in the drying chamber 15. The drying chamber 15 was divided into four sections, and drying air of 120 ° C., 130 ° C., 130 ° C., and 130 ° C. was supplied from the blower (not shown) from the upstream side. The conveying tension of the film 52 by the roller 54 was set to 100 N / m, and the film was dried for about 10 minutes until the residual solvent amount finally reached 0.3% by mass. The wrap angle of the roller 54 (film winding center angle) was 90 degrees and 180 degrees (shown exaggerated in FIG. 1). The material of the roller 54 was made of aluminum or carbon steel, and the surface thereof was subjected to hard chrome plating. As the roller 54, a roller having a flat surface shape and a roller matted by blasting were used. All film position fluctuations due to the rotation of the roller 54 were 50 μm or less. The roller deflection at a tension of 100 N / m was selected to be 0.5 mm or less.

  The solvent gas contained in the drying chamber 15 was removed by adsorption using the adsorption / recovery device 55. The adsorbent used here was activated carbon, and desorption was performed using dry nitrogen. The recovered solvent was reused as a dope preparation solvent with the water content adjusted to 0.3 mass% or less. The drying air contains plasticizers, UV absorbers and other high-boiling substances in addition to the solvent gas, so these were removed by a cooler and pre-adsorber to be removed by cooling and used for recycling. And adsorption / desorption conditions were set so that VOC (volatile organic compound) in the outdoor exhaust gas was finally 10 ppm or less. Moreover, the solvent amount collect | recovered by a condensation method among all the evaporation solvents was 90 mass%, and most of the remainder was collect | recovered by adsorption collection.

  The dried film 52 was conveyed to a first humidity control chamber (not shown). A drying air of 110 ° C. was supplied to the transition portion between the drying chamber 15 and the first humidity control chamber. Air having a temperature of 50 ° C. and a dew point of 20 ° C. was supplied to the first humidity control chamber. Further, the film 52 was conveyed to a second humidity control chamber (not shown) that suppresses the curling of the film 52. In the second humidity control chamber, air of 90 ° C. and humidity of 70% was directly applied to the film 52.

  The film 52 after humidity control was cooled to 30 ° C. or lower in the cooling chamber 16, and then subjected to ear cutting at both ends again with an ear cutting device (not shown). The charged voltage of the film 52 being conveyed was adjusted by installing a forced charge removal device (charge removal bar) 56 so that the voltage was always in the range of −3 kV to +3 kV. Further, knurling was applied to both ends of the film 52 by a knurling roller 57. The knurling is imparted by embossing from one side of the film 52, the width for imparting the knurling is 10 mm, and the pressure applied by the knurling roller so that the height of the unevenness is 12 μm higher than the average thickness of the film 52 on average. It was set.

  Then, the film 52 was conveyed to the winding chamber 17. The air conditioning of the winding chamber 17 was maintained at a room temperature of 28 ° C. and a humidity of 70%. Inside the winding chamber 17, an ion wind static eliminating device (not shown) was also installed so that the charged voltage of the film 52 was −1.5 kV to +1.5 kV. The product width of the film (thickness 40 μm) 52 thus obtained was 1475 mm. The diameter of the winding roller 58 was 169 mm. The tension pattern was such that the winding start tension was 300 N / m and the winding end was 200 N / m. The total winding length was 4000 m. The variation range of winding deviation at the time of winding (sometimes referred to as the oscillating width) was ± 5 mm, and the winding deviation period with respect to the winding roller 58 was 400 m. The pressing pressure of the press roller 59 against the take-up roller 58 was set to 50 N / m. The temperature of the film 52 at the time of winding was 25 ° C., the water content was 1.4% by mass, and the residual solvent amount was 0.3% by mass. The average drying rate was 20% by mass (dry weight reference solvent) / min throughout the entire process. There was no winding looseness, no wrinkles, and no slippage occurred in the impact test at 10G. The roll appearance was also good.

  The film roll of the film 52 was stored in a storage rack at 25 ° C. and 55% RH for 1 month and further examined in the same manner as described above. As a result, no significant change was observed. Further, no adhesion was observed in the roll. In addition, after the film 52 was formed, no peeling residue of the cast film 39 was observed on the rotating drum 31.

The thickness unevenness of the film 52 was measured by the following method, and the following evaluation was performed. As a measuring method, the film 52 was measured at 5 points using an electronic micrometer manufactured by Anritsu Electric Co., Ltd. at 25 ° C. and 60 RH%. The relative standard deviation RSD (= deviation / average value × 100%) was calculated from the average value and deviation of the measured values. The film thickness unevenness was evaluated by a four-step evaluation from the relative standard deviation.
Less than 5% ・ Excellent uniformity of thickness (◎).
5% or more and less than 10%. Excellent thickness uniformity (◯).
10% or more and less than 15% ・ Slight thickness unevenness occurs, but there is no problem as a product (Δ).
15% or more ··· Thickness unevenness occurs and cannot be used as a product (x).

  Experiment 2 was performed under the same conditions as Experiment 1, except that the number of decompression chambers was two and the clearance CL was 0.7 mm. Experiment 3 was performed under the same conditions as Experiment 1, except that three decompression chambers and a clearance CL of 0.7 mm were used. In Experiment 4, the experiment was performed under the same conditions as Experiment 1 except that the number of decompression chambers was 8 and the clearance CL was 0.2 mm. In Experiment 5, the experiment was performed under the same conditions as Experiment 1 except that the number of decompression chambers was three, the clearance CL was 0.2 mm, and the degree of decompression of the casting bead back surface 38a was −400 Pa. In Experiment 6, the experiment was performed under the same conditions as Experiment 1, except that the number of decompression chambers was three, the clearance CL was 0.5 mm, and the degree of decompression was −400 Pa.

In Experiment 7, a dope B was prepared from the following formulation under the same conditions as in Experiment 1.
Cellulose triacetate (substitution degree 2.84, viscosity average polymerization degree 306, water content 0.2 mass%, viscosity 6 mass% in dichloromethane solution 315 mPa · s, average particle diameter 1.5 mm with standard deviation 0.5 mm Some powder) 20 parts by mass Methyl acetate 58 parts by mass Acetone 5 parts by mass Methanol 10 parts by mass 1-propanol 5 parts by mass Plasticizer A (triphenyl phosphate) 1.2 parts by mass Plasticizer B (diphenyl phosphate) 2 parts by mass UV agent a: 2 (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole 0.2 part by mass UV agent b: 2 (2′-hydroxy-3 ′, 5 ′ -Di-tert-amylphenyl) -5
Chlorbenzotriazole 0.2 parts by mass of citric acid ester mixture (citric acid, monoethyl ester, diethyl ester, triethyl ester mixture) 0.02 parts by mass of fine particles (silicon dioxide (average particle size 15 nm), Mohs hardness about 7) 0. 05 parts by mass

  In Experiment 7, the experiment was performed under the same conditions as Experiment 1 except that the dope B was used.

  In Experiment 8, the experiment was performed under the same conditions as Experiment 7 except that the decompression chamber was two chambers and the clearance CL was 0.7 mm. In Experiment 9, the experiment was performed under the same conditions as Experiment 7 except that the decompression chamber was set to three chambers and the clearance CL was set to 0.7 mm. In Experiment 10, the experiment was performed under the same conditions as Experiment 8 except that the decompression chamber was 8 chambers and the clearance CL was 0.2 mm.

  In Experiment 1 to Experiment 10 according to the present invention, the clearance between the metal support on the back of the casting bead and the drum is 0.2 mm to 0.7 mm, and the number of chamber zones is 2 to 8, so that the thickness unevenness of the manufactured film is reduced. We were able to create conditions that were both suppressed and suitable for manufacturing.

In Experiments 11 to 15, which are comparative examples, each experiment was performed under the same conditions as Experiment 1 except for the experimental conditions shown in Table 2 below. Moreover, in Experiment 16 thru | or Experiment 20 which is a comparative example, each experiment was conducted on the same conditions as Experiment 7 except the experimental conditions of Table 2 shown later. After the show together with in each experimental condition and uneven thickness and manufacturing aptitude.

  From Experiment 11 and Experiment 16, when the clearance CL between the metal support and the chamber was wide, entrained air from the rear of the casting bead hit the casting bead back surface 38a, and thickness unevenness occurred. Further, the formation of the casting bead 38 became unstable, and the production could not be maintained.

  If the decompression chamber was not divided from Experiment 12 and Experiment 17, the entrained wind from the rear of the casting bead could not be shut out, and the film had uneven thickness.

  From Experiment 13 and Experiment 18, when no exhaust port was installed in each decompression chamber, the flow of the accompanying air could not be controlled, and the film had uneven thickness.

  From Experiment 14, Experiment 15, Experiment 19, and Experiment 20, when the number of decompression chambers was large, the film thickness unevenness became good, but the gas in which the organic solvent volatilized stayed in the decompression chamber, resulting in condensation failure. .

It is the schematic of the film manufacturing line for enforcing the solution casting method of this invention. It is a principal part enlarged view of the film manufacturing line of FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Film production line 30 Casting die 31 Rotating drum 36 Depressurization chamber 37 Depressurization device 38 Casting bead 38a Casting bead back surface 52 Film CL Clearance between support and decompression chamber

Claims (4)

In a solution casting method in which a dope containing a polymer and a solvent is cast on a support by forming a casting bead from a casting die and then peeled off from the support as a film,
Inside the is divided by the mobile Direction support multiple decompression chamber by Rukoto is formed, using a low pressure chamber that push reduced the support contact surface side of the bead,
The gap between the decompression chamber and the support is in the range of 0.05 mm to 3 mm ,
Among the plurality of decompression chambers capable of independently adjusting the degree of decompression, the decompression chamber on the upstream side in the moving direction of the support is set to a decompression degree lower than that on the downstream decompression chamber. A solution casting method. When the maximum value of the absolute pressure of each decompression chamber is Pn (Pa),
Solution casting method according to claim 1, characterized in that the pressure of the pressure-reducing chamber to a range of less than 0.9 × Pn (Pa) over 1 × Pn (Pa). The solution casting method according to claim 1 or 2 , wherein the number of the decompression chambers is 2 or more and 10 or less . The solution casting method according to claim 1, wherein each decompression chamber is provided with an exhaust port.

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